Metal complexes contanining acetylenic ligands, polymerization catalysts and addition polymerization process

ABSTRACT

A complex of a Group 3-10 metal, said complex comprising a cyclic group containing delocalized electrons, a bridging group connecting he metal with the cyclic group, and acetylene or a derivative thereof

[0001] This invention relates to a class of metal complexes and toaddition polymerization catalysts derived from such complexes that areparticularly suitable for use in a polymerization process for preparinghomopolymers and copolymers of olefins or diolefins, includingcopolymers comprising two or more olefins or diolefins such ascopolymers comprising a monovinyl aromatic monomer and ethylene or aC₃₋₈ α-olefin and ethylene.

[0002] Constrained geometry metal complexes and methods for theirpreparation are disclosed in U.S. Pat. No. 5,703,187. Additionalteachings of constrained geometry catalysts may be found in U.S. Pat.Nos. 5,321,106, 5,721,185, 5,374,696, 5,470,993, 5,541,349, and U.S.Pat. No. 5,486,632. Such metal complexes containing a neutral conjugateddiene ligand group are disclosed in U.S. Pat. Nos. 5,470,993, 5,556,928and 5,624,878.

[0003] Certain highly active, polyaromatic, metal complexes, especiallyderivatives of cyclopentaphenanthrenyl ligand groups are disclosed inU.S. Pat. No. 6,150,297. Metallocenes containing multiple, non-aromaticfused ring systems are disclosed in U.S. application Ser. No.09/879,463, filed Jun. 12, 2001.

[0004] According to the present invention there is provided a metalcomplex corresponding to the formula: CpM(ZY)L (I),

[0005] where Cp is a neutral or anionic ligand group containing at leaston cyclic group containing delocalized π-electrons, by means of which Cpis bonded to M;

[0006] M is a metal selected from Groups 3-10 or the Lanthanide seriesof the Periodic Table of the Elements;

[0007] ZY is a linking group with Z bonded to Cp and Y bonded to M, andwherein Z is SiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶₂, BR⁶, BR⁶L″, SnR⁶, or GeR⁶ ₂, and

[0008] Y is —O—, —S—, —NR⁵—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂;

[0009] R⁵, independently each occurrence, is hydrocarbyl,trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, said R⁵ havingup to 20 atoms not counting hydrogen, and optionally two R⁵ groupstogether with the remainder of Y form a ring system;

[0010] R⁶, independently each occurrence, is hydrogen, or a memberselected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl,halogenated aryl, —NR⁷ ₂, and combinations thereof, said R⁶ having up to20 atoms not counting hydrogen, and optionally, one or more R⁶ groupstogether with the remainder of Z form a ring system;

[0011] R⁷ independently each occurrence is hydrocarbyl or two R⁷ groupstogether with N form a ring system, said R⁷ having up to 10 atoms notcounting hydrogen;

[0012] L″ is a monodentate or polydentate Lewis base optionally bondedto R⁶; and

[0013] L is acetylene, or a mono- or di-substituted derivative ofacetylene.

[0014] The above compounds may exist as isolated crystals, as a mixturewith other compounds, in the form of a solvated adduct, dissolved in asolvent, especially an organic liquid solvent, in the form of a dimer,or as a chelated derivative, especially wherein the chelating agent isan organic material such as ethylenediaminetetraacetic acid (EDTA).

[0015] Also, according to the present invention, there is provided acatalyst for addition polymerizations comprising:

[0016] A.

[0017] i) a metal complex of formula (I), and

[0018] ii) an activating cocatalyst, the molar ratio of i) to ii) beingfrom 1:10,000 to 100:1, or

[0019] B.

[0020] the reaction product formed by converting a metal complex offormula (I) to an active catalyst by use of the foregoing combination orby use of an activating technique.

[0021] Further according to the present invention there is provided aprocess for the polymerization of addition polymerizable monomers,especially one or more olefins comprising contacting the monomer ormixture of monomers, under polymerization conditions with a catalystcomprising:

[0022] A.

[0023] i) a metal complex of formula (I), and

[0024] ii) an activating cocatalyst, the molar ratio of i) to ii) beingfrom 1:10,000 to 100:1, or

[0025] B.

[0026] the reaction product formed by converting a metal complex offormula (I) to an active catalyst by use of the foregoing combination orby use of an activating technique.

[0027] Use of the present catalysts and processes is especiallyefficient in production of olefin homopolymers, copolymers of two ormore olefins, in particular, copolymers of ethylene and a vinylaromaticmonomer, such as styrene, and interpolymers of three or morepolymerizable monomers over a wide range of polymerization conditions,and especially at elevated temperatures. They are especially useful forthe formation of ethylene homopolymers, copolymers of ethylene and oneor more higher α-olefins (that is, olefins having 3 or more carbonatoms), copolymers of ethylene, propylene and a diene (EPDM copolymers),copolymers of ethylene and vinylaromatic monomers such as styrene (ESpolymers), copolymers of ethylene, styrene, and a diene (ESDM polymers),and copolymers of ethylene, propylene and styrene (EPS polymers).Examples of suitable diene monomers include ethylidenenorbornene,1,4-hexadiene or similar conjugated or nonconjugated dienes.Surprisingly, the metal complexes of formula (II) demonstrate equivalentor improved catalytic properties compared to metal complexes containingpolycyclic, fully aromatic, hydrocarbon ligands, and they and theirdegradation products are more biologically inert compared to compoundscontaining fused, polycyclic, fully aromatic hydrocarbon ligands.

[0028] The catalysts of this invention may also be supported on a solidmaterial and used in olefin polymerization processes, includingsolution, slurry or gas phase polymerization processes. The catalyst maybe used in combination with one or more additional polymerizationcatalysts including other metal complexes or conventional Ziegler-Nattacatalysts, in the same or different polymerization reactors, operatingin series or in parallel. Finally, the catalyst may be prepolymerizedwith one or more olefin monomers in situ in a polymerization reactor orin a separate process with intermediate recovery of the prepolymerizedcatalyst prior to the primary polymerization process.

[0029] In addition to their use as addition polymerization catalysts,complexes according to the present invention may be used forhydroformulation, hydrogenation or oligomerization processes.

[0030] All reference to the Periodic Table of the Elements herein shallrefer to the Periodic Table of the Elements, published and copyrightedby CRC Press, Inc., 1995. Also, any reference to a Group or Groups shallbe to the Group or Groups as reflected in this Periodic Table of theElements using the IUPAC system for numbering groups. The contents ofany patent, patent application or publication referenced herein ishereby incorporated by reference in its entirety herein, especially withrespect to its disclosure of organometallic structures, synthetictechniques and general knowledge in the art. As used herein the term“aromatic” refers to a polyatomic, cyclic, ring system containing (4δ+2)π-electrons, wherein δ is an integer greater than or equal to 1. Theterm “fused” as used herein with respect to two polyatomic, cyclic ringsmeans that such rings have two adjacent atoms thereof common to bothrings. The term “fused” as used herein with respect to a ring systemcontaining more than two polyatomic, cyclic rings, means that at leasttwo rings thereof are fused together.

[0031] Desirably, in the compounds of the invention, Cp is acyclopentadienyl group or a hydrocarbyl substituted derivative thereof,including fused multiple ring groups. Preferred L″ groups are carbonmonoxide; phosphines, especially trimethylphosphine, triethylphosphine,triphenylphosphine and bis(1,2-dimethylphosphino)ethane; P(OR⁴)₃,wherein R⁴ is C₁₋₂₀ hydrocarbyl; ethers, especially tetrahydrofuran;amines, especially pyridine, bipyridine, tetramethylethylenediamine(TMEDA), and triethylamine; olefins; and neutral conjugated dieneshaving from 4 to 40, preferably 5 to 40 carbon atoms.

[0032] Preferred metal complexes of formula (I) correspond to theformula:

[0033] wherein

[0034] M is a group 4 metal, preferably titanium;

[0035] Y is NR , wherein R⁵ is C₁₋₁₀ alkyl or cycloalkyl;

[0036] Z is dimethylsilane;

[0037] J independently each occurrence is hydrogen, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy,trihydrocarbylsiloxy, bis(trihydrocarbylsilyl)amino,di(hydrocarbyl)amino, hydrocarbyleneamino, hydrocarbylimino,di(hydrocarbyl)phosphino, hydrocarbylenephosphino, hydrocarbylsulfido,halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said J group having up to 40atoms not counting hydrogen atoms, and optionally two J groups togethermay form a divalent derivative thereby forming a saturated orunsaturated ring; and

[0038] L is a disubstituted acetylene compound of the formula, J′C≡CJ′,wherein J′ is hydrocarbyl or tri(hydrocarbylsilyl) of up to 10 atoms notcounting hydrogen, preferably trimethylsilyl. Because the ligand, L, isneutral, the Group 4 metal, preferably Ti, is in the +2 formal oxidationstate.

[0039] The preparation of the metal complexes of formula (I) isstraightforward, using standard techniques of ligand formation andorganometallic synthesis. In one technique, the corresponding alkylsubstituted metal complex is contacted with acetylene or a substitutedacetylene in the presence of an oxidizing agent, especially an alkalimetal compound.

[0040] Illustrative metal complexes that may be employed in the practiceof the present invention include:

[0041](tetramethylcyclopentadienyl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,

[0042] (tetramethylcyclopentadienyl)-N-(cyclohexyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,

[0043] (inden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium(II) 1,2-bis(trimethylsilyl)acetylene,

[0044] (inden-1-yl)-N-(cyclohexyl)dimethylsilanamide titanium (II)1,2-bis(trimethylsilyl)acetylene,

[0045](2-methyl-4-phenylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,

[0046] (2-methyl-4-phenylinden-1-yl)-N-(cyclohexyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,

[0047](2-methyl-4-naphthylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,

[0048] (2-methyl-4-naphthylinden-1-yl)-N-(cyclohexyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,

[0049](3-(N,N-dimethylamino)inden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,

[0050](3-(N,N-dimethylamino)inden-1-yl)-N-(cyclohexyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,

[0051](3-(N,N-dimethylamino)inden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,

[0052] (3-(N-pyrrolidino)inden-1-yl)-N-(cyclohexyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,

[0053](3-(N-pyrrolidino)inden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,

[0054](3-(N,N-dimethylamino)inden-1-yl)-N-(cyclohexyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,

[0055] (s-inden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium(II) 1,2-bis(trimethylsilyl)acetylene,

[0056] (s-inden-1-yl)-N-(cyclohexyl)dimethylsilanamide titanium (II)1,2-bis(trimethylsilyl)acetylene,(3,4-(cyclopenta(l)phenantrathen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,

[0057](3,4-(cyclopenta(l)phenantrathen-2-yl)-N-(cyclohexyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,

[0058](2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,2acetylene,bis(trimethylsilyl)acetylene, and

[0059](2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,

[0060] and mixtures thereof, especially mixtures of positional isomers.

[0061] The skilled artisan will recognize that additional members of theforegoing list, obtainable by substitution of known ligands or differentGroup 3-10 metals for those specifically named, are also included withinthe invention. Moreover, it should also be recognized that all possibledelocalized electronic distributions within the π-bonded, cyclic,ligand, such as η³, η⁴ or η⁵ are intended to be included by theforegoing named compounds.

[0062] The complexes can be prepared by combining a Group 3-10, metalsalt with the corresponding cyclic ligand silane amide dianion in aninert diluent, or by combining a metal amide with the correspondingneutral, cyclic, silane substituted ring system in an inert diluent. Areducing agent can be employed to produce the lower oxidation statecomplexes, and standard ligand exchange procedures can by used toproduce different ligand substituents. Processes that are suitablyadapted for use herein are well known to synthetic organometallicchemists. The syntheses are preferably conducted in a suitablenoninterfering solvent at a temperature from −100 to 300° C., preferablyfrom −78 to 100° C., most preferably from 0 to 50° C. By the term“reducing agent” herein is meant a metal or compound which, underreducing conditions causes the metal M, to be reduced from a higher to alower oxidation state. Examples of suitable metal reducing agents arealkali metals, alkaline earth metals, aluminum, zinc, alloys of alkalimetals or alkaline earth metals such as sodium/mercury amalgam andsodium/potassium alloy. Examples of suitable reducing agent compoundsare sodium naphthalenide, potassium graphite, lithium alkyls, lithium orpotassium alkadienyls; dialkylmagnesium compounds, and Grignardreagents. Most preferred reducing agents are the alkali metals oralkaline earth metals, especially lithium and magnesium metal.

[0063] Suitable reaction media for the formation of the complexesinclude aliphatic and aromatic hydrocarbons, ethers, and cyclic ethers,particularly branched-chain hydrocarbons such as isobutane, butane,pentane, hexane, heptane, octane, and mixtures thereof; cyclic andalicyclic hydrocarbons such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof; aromaticand hydrocarbyl-substituted aromatic compounds such as benzene, toluene,and xylene, C₁₋₄ dialkyl ethers, C₁₋₄ dialkyl ether derivatives of(poly)alkylene glycols, and tetrahydrofuran. Mixtures of the foregoingare also suitable.

[0064] The complexes are rendered catalytically active by combinationwith an activating cocatalyst or use of an activating technique, such asthose that are previously known in the art for use with Group 4 metalolefin polymerization complexes. Suitable activating cocatalysts for useherein include polymeric or oligomeric alumoxanes, especiallymethylalumoxane, triisobutyl aluminum modified methylalumoxane, orisobutylalumoxane; neutral Lewis acids, such as C₁₋₃₀ hydrocarbylsubstituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- ortri(hydrocarbyl)boron compounds and halogenated (includingperhalogenated) derivatives thereof, having from 1 to 10 carbons in eachhydrocarbyl or halogenated hydrocarbyl group, more especiallyperfluorinated tri(aryl)boron compounds, and most especiallytris(pentafluorophenyl)borane; nonpolymeric, compatible,noncoordinating, ion forming compounds (including the use of suchcompounds under oxidizing conditions), especially the use of ammonium-,phosphonium-, oxonium-, carbonium-, silylium- or sulfonium- salts ofcompatible, noncoordinating anions, or ferrocenium salts of compatible,noncoordinating anions; bulk electrolysis (explained in more detailhereinafter); and combinations of the foregoing activating cocatalystsand techniques. A preferred ion forming compound is atri(C₁₋₂₀-hydrocarbyl)ammonium salt of a tetrakis(fluoroaryl)borate,especially a tetrakis(pentafluorophenyl)borate. The foregoing activatingcocatalysts and activating techniques have been previously taught withrespect to different metal complexes in the following references:EP-A-277,003, U.S. Pat. Nos. 5,153,157, 5,064,802, 5,321,106, 5,721,185,5,350,723, 5,425,872, 5,625,087, 5,883,204, 5,919,983, 5,783,512, WO99/15534, and U.S. Ser. No. 09/251,664, filed Feb. 17, 1999(WO99/42467).

[0065] Combinations of neutral Lewis acids, especially the combinationof a trialkylaluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to20 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, further combinations of such neutralLewis acid mixtures with a polymeric or oligomeric alumoxane, andcombinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxaneare especially desirable activating cocatalysts. Preferred molar ratiosof Group 4 metal complex:tris(pentafluorophenylborane:alumoxane are from1:1:1 to 1:10:30, more preferably from 1:1:1.5 to 1:5:10.

[0066] Suitable ion forming compounds useful as cocatalysts in oneembodiment of the present invention comprise a cation which is a Brnstedacid capable of donating a proton, and a compatible, noncoordinatinganion, A⁻. As used herein, the term “noncoordinating” means an anion orsubstance which either does not coordinate to the Group 4 metalcontaining precursor complex and the catalytic derivative derivedtherefrom, or which is only weakly coordinated to such complexes therebyremaining sufficiently labile to be displaced by a neutral Lewis base. Anoncoordinating anion specifically refers to an anion which whenfunctioning as a charge balancing anion in a cationic metal complex doesnot transfer an anionic substituent or fragment thereof to said cationthereby forming neutral complexes. “Compatible anions” are anions whichare not degraded to neutrality when the initially formed complexdecomposes and are noninterfering with desired subsequent polymerizationor other uses of the complex.

[0067] Preferred anions are those containing a single coordinationcomplex comprising a charge-bearing metal or metalloid core which anionis capable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitrites. Suitable metals include,but are not limited to, aluminum, gallium, niobium or tantalum. Suitablemetalloids include, but are not limited to, boron, phosphorus, andsilicon. Compounds containing anions which comprise coordinationcomplexes containing a single metal or metalloid atom are, of course,well known and many, particularly such compounds containing a singleboron atom in the anion portion, are available commercially.

[0068] Preferably such cocatalysts may be represented by the followinggeneral formula:

(L*−H)_(d) ⁺(A)^(d−)

[0069] wherein:

[0070] L* is a neutral Lewis base;

[0071] (L*−H)⁺ is a conjugate Brnsted acid of L*;

[0072] A^(d−) is a noncoordinating, compatible anion having a charge ofd−, and

[0073] d is an integer from 1 to 3.

[0074] More preferably A^(d−) corresponds to the formula: [M′Q₄]⁻;

[0075] wherein:

[0076] M′ is boron or aluminum in the +3 formal oxidation state; and

[0077] Q independently each occurrence is selected from hydride,dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halo-substitutedhydrocarbyl, halo-substituted hydrocarbyloxy, and halo-substitutedsilylhydrocarbyl radicals (including perhalogenatedhydrocarbyl-perhalogenated hydrocarbyloxy- and perhalogenatedsilylhydrocarbyl radicals), said Q having up to 20 carbons with theproviso that in not more than one occurrence is Q halide. Examples ofsuitable hydrocarbyloxide Q groups are disclosed in U.S. Pat. No.5,296,433.

[0078] In a more preferred embodiment, d is one, that is, the counterion has a single negative charge and is A⁻. Activating cocatalystscomprising boron which are particularly useful in the preparation ofcatalysts of this invention may be represented by the following generalformula:

(L*−H)⁺(BQ₄)⁻;

[0079] wherein:

[0080] L* is as previously defined;

[0081] B is boron in a formal oxidation state of 3; and

[0082] Q is a hydrocarbyl-, hydrocarbyloxy-, fluorohydrocarbyl-,fluorohydrocarbyloxy-, hydroxyfluorohydrocarbyl-,dihydrocarbylaluminumoxyfluorohydrocarbyl-, or fluorinatedsilylhydrocarbyl-group of up to 20 nonhydrogen atoms, with the provisothat in not more than one occasion is Q hydrocarbyl. Most preferably, Qis each occurrence a fluorinated aryl group, especially, apentafluorophenyl group.

[0083] Preferred Lewis base salts are ammonium salts, more preferablytrialkyl-ammonium- or dialkylarylammonium- salts containing one or moreC₁₂₋₄₀ alkyl groups. The latter cocatalysts have been found to beparticularly suitable for use in combination with not only the presentmetal complexes but other Group 4 metallocenes as well.

[0084] Illustrative, but not limiting, examples of boron compounds whichmay be used as an activating cocatalyst in the preparation of theimproved catalysts of this invention (as well as previously known Group4 metal catalysts) are tri-substituted ammonium salts such as:

[0085] trimethylammonium tetrakis(pentafluorophenyl) borate,

[0086] triethylammonium tetrakis(pentafluorophenyl) borate,

[0087] tripropylammonium tetrakis(pentafluorophenyl) borate,

[0088] tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate,

[0089] tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate,

[0090] N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate,

[0091] N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate,

[0092] N,N-dimethylanilinium benzyltris(pentafluorophenyl) borate,

[0093] N,N-dimethylaniliniumtetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl) borate,

[0094] N,N-dimethylaniliniumtetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl) borate,

[0095] N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl)borate,

[0096] N,N-diethylanilinium tetrakis(pentafluorophenyl) borate,

[0097] N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate,

[0098] dimethyltetradecylammonium tetrakis(pentafluorophenyl) borate,

[0099] dimethylhexadecylammonium tetrakis(pentafluorophenyl) borate,

[0100] dimethyloctadecylammonium tetrakis(pentafluorophenyl) borate,

[0101] methylditetradecylammonium tetrakis(pentafluorophenyl) borate,

[0102] methylditetradecylammonium (hydroxyphenyl)tris(pentafluorophenyl)borate,

[0103] methylditetradecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

[0104] methyldihexadecylammonium tetrakis(pentafluorophenyl) borate,

[0105] methyldihexadecylammonium (hydroxyphenyl)tris(pentafluorophenyl)borate,

[0106] methyldihexadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

[0107] methyldioctadecylammonium tetrakis(pentafluorophenyl) borate,

[0108] methyldioctadecylammonium (hydroxyphenyl)tris(pentafluorophenyl)borate,

[0109] methyldioctadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

[0110] methyldioctadecylammonium tetrakis(pentafluorophenyl) borate,

[0111] phenyldioctadecylammonium tetrakis(pentafluorophenyl) borate,

[0112] phenyldioctadecylammonium (hydroxyphenyl)tris(pentafluorophenyl)borate,

[0113] phenyldioctadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

[0114] (2,4,6-trimethylphenyl)dioctadecylammoniumtetrakis(pentafluorophenyl)borate,

[0115] (2,4,6-trimethylphenyl)dioctadecylammonium(hydroxyphenyl)tris(pentafluorophenyl)borate,

[0116] (2,4,6-trimethylphenyl)dioctadecylammonium(diethylaluminoxyphenyl) tris(pentafluorophenyl)borate,

[0117] (2,4,6-trifluorophenyl)dioctadecylammoniumtetrakis(pentafluorophenyl)borate,

[0118] (2,4,6-trifluorophenyl)dioctadecylammonium(hydroxyphenyl)tris(pentafluorophenyl)borate,

[0119] (2,4,6-trifluorophenyl)dioctadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

[0120] (pentafluorophenyl)dioctadecylammoniumtetrakis(pentafluorophenyl)borate,

[0121] (pentafluorophenyl)dioctadecylammonium(hydroxyphenyl)tris(pentafluorophenyl)borate,

[0122] (pentafluorophenyl)dioctadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

[0123] (p-trifluoromethylphenyl)dioctadecylammoniumtetrakis(pentafluorophenyl)borate,

[0124] (p-trifluoromethylphenyl)dioctadecylammonium(hydroxyphenyl)tris(pentafluorophenyl) borate,

[0125] (p-trifluoromethylphenyl)dioctadecylammonium(diethylaluminoxyphenyl)tris(penta-fluorophenyl) borate,

[0126] p-nitrophenyldioctadecylammoniumtetrakis(pentafluorophenyl)borate,

[0127] p-nitrophenyldioctadecylammonium(hydroxyphenyl)tris(pentafluorophenyl) borate,

[0128] p-nitrophenyldioctadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

[0129] and mixtures of the foregoing,

[0130] dialkyl ammonium salts such as:

[0131] di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate,methyloctadecylammonium tetrakis(pentafluorophenyl) borate,methyloctadodecylammonium tetrakis(pentafluorophenyl) borate, anddioctadecylammonium tetrakis(pentafluorophenyl) borate;

[0132] tri-substituted phosphonium salts such as:

[0133] triphenylphosphonium tetrakis(pentafluorophenyl) borate,methyldioctadecylphosphonium tetrakis(pentafluorophenyl) borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate;

[0134] di-substituted oxonium salts such as:

[0135] diphenyloxonium tetrakis(pentafluorophenyl) borate,di(o-tolyl)oxonium tetrakis(pentafluorophenyl) borate, anddi(octadecyl)oxonium tetrakis(pentafluorophenyl) borate;

[0136] di-substituted sulfonium salts such as:

[0137] di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and

[0138] methylcotadecylsulfonium tetrakis(pentafluorophenyl) borate.

[0139] Preferred trialkylammonium cations are methyldioctadecylammoniumand dimethyloctadecylammonium. The use of the above Brnsted acid saltsas activating cocatalysts for addition polymerization catalysts is knownin the art, having been disclosed in U.S. Pat. Nos. 5,064,802,5,919,983, 5,783,512 and elsewhere. Preferred dialkylarylammoniumcations are fluorophenyldioctadecylammonium-,perfluoro-phenyldioctacecylammonium- andp-trifluoromethylphenyldi(octadecyl)ammonium cations. It should be notedthat certain of the cocatalysts, especially those containing ahydroxyphenyl ligand in the borate anion, may require the addition of aLewis acid, especially a trialkylaluminum compound, to thepolymerization mixture or the catalyst composition, in order to form theactive catalyst composition.

[0140] Another suitable ion forming, activating cocatalyst comprises asalt of a cationic oxidizing agent and a noncoordinating, compatibleanion represented by the formula:

(Ox^(e+))_(d)(A^(d−))_(e−)

[0141] wherein:

[0142] Ox^(e+) is a cationic oxidizing agent having a charge of e+;

[0143] e is an integer from 1 to 3; and

[0144] A^(d−) and d are as previously defined.

[0145] Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺ or Pb⁺². Preferred embodimentsof A^(d−) are those anions previously defined with respect to theBrnsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate. The use of the above salts asactivating cocatalysts for addition polymerization catalysts is known inthe art, having been disclosed in U.S. Pat. No. 5,321,106.

[0146] Another suitable ion forming, activating cocatalyst comprises acompound which is a salt of a carbenium ion and a noncoordinating,compatible anion represented by the formula:

{circle over (C)}⁺A⁻

[0147] wherein:

[0148] {circle over (C)}⁺ is a C₁₋₂₀ carbenium ion; and

[0149] A⁻ is as previously defined. A preferred carbenium ion is thetrityl cation, that is triphenylmethylium. The use of the abovecarbenium salts as activating cocatalysts for addition polymerizationcatalysts is known in the art, having been disclosed in U.S. Pat. No.5,350,723.

[0150] A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:

R³ ₃Si(X′)_(q) ⁺A⁻

[0151] wherein:

[0152] R³ is C₁₋₁₀ hydrocarbyl, and X′, q and A⁻ are as previouslydefined.

[0153] Preferred silylium salt activating cocatalysts aretrimethylsilylium tetrakispentafluorophenylborate, triethylsilyliumtetrakispentafluorophenylborate and ether substituted adducts thereof.The use of the above silylium salts as activating cocatalysts foraddition polymerization catalysts is known in the art, having beendisclosed in U.S. Pat. No. 5,625,087.

[0154] Certain complexes of alcohols, mercaptans, silanols, and oximeswith tris(pentafluorophenyl)borane are also effective catalystactivators and may be used according to the present invention. Suchcocatalysts are disclosed in U.S. Pat. No. 5,296,433.

[0155] Another class of suitable catalyst activators are expandedanionic compounds corresponding to the formula: (A^(1+a) _(¹) )_(b)¹(Z¹J¹ _(j) _(¹) )^(−c1) _(d) _(¹) ,

[0156] wherein:

[0157] A¹ is a cation of charge +a¹,

[0158] Z¹ is an anion group of from 1 to 50, preferably 1 to 30 atoms,not counting hydrogen atoms, further containing two or more Lewis basesites;

[0159] J¹ independently each occurrence is a Lewis acid coordinated toat least one Lewis base site of Z¹, and optionally two or more such J¹groups may be joined together in a moiety having multiple Lewis acidicfunctionality,

[0160] j¹ is a number from 2 to 12 and

[0161] a¹, b¹, c¹, and d¹ are integers from 1 to 3, with the provisothat a¹×b¹ is equal to c¹×d¹.

[0162] The foregoing cocatalysts (illustrated by those havingimidazolide, substituted imidazolide, imidazolinide, substitutedimidazolinide, benzimidazolide, or substituted benzimidazolide anions)may be depicted schematically as follows:

[0163] wherein:

[0164] A¹⁺ is a monovalent cation as previously defined, and preferablyis a trihydrocarbyl ammonium cation, containing one or two C₁₀₋₄₀ alkylgroups, especially the methylbis(tetradecyl)ammonium- ormethylbis(octadecyl)ammonium-cation,

[0165] R⁸, independently each occurrence, is hydrogen or a halo,hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl,(including mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atomsnot counting hydrogen, preferably C₁₋₂₀ alkyl, and

[0166] J¹ is tris(pentafluorophenyl)borane ortris(pentafluorophenyl)aluminane.

[0167] Examples of these catalyst activators include thetrihydrocarbylammonium-, especially, methylbis(tetradecyl)ammonium- ormethylbis(octadecyl)ammonium-salts of:

[0168] bis(tris(pentafluorophenyl)borane)imidazolide,

[0169] bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide,bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide,bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide,

[0170] bis(tris(pentafluorophenyl)borane)4,5-bis(heptadecyl)imidazolide,

[0171] bis(tris(pentafluorophenyl)borane)imidazolinide,

[0172] bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide,bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide,bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide,

[0173]bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide,

[0174] bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide,

[0175]bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide,

[0176] bis(tris(pentafluorophenyl)alumane)imidazolide,

[0177] bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide,bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide,bis(tris(pentafluorophenyl)alumane)4,5-bis(undecyl)imidazolide,

[0178]bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide,

[0179] bis(tris(pentafluorophenyl)alumane)imidazolinide,

[0180] bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide,bis(tris(pentafluorophenyl)alumane)4,5-bis(undecyl)imidazolinide,

[0181]bis(tris(pentafluorophenyl)alumane)4,5-bis(heptadecyl)imidazolinide,

[0182] bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide,and

[0183]bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.

[0184] A further class of suitable activating cocatalysts includecationic Group 13 salts corresponding to the formula:

[M″Q¹ ₂L′_(1′)]⁺(Ar^(f) ₃M′Q²)⁻

[0185] wherein:

[0186] M″ is aluminum, gallium, or indium;

[0187] M′ is boron or aluminum;

[0188] Q′ is C₁₋₂₀ hydrocarbyl, optionally substituted with one or moregroups which independently each occurrence are hydrocarbyloxy,hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino,hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, orhydrocarbylsulfido groups having from 1 to 20 atoms other than hydrogen,or, optionally, two or more Q¹ groups may be covalently linked with eachother to form one or more fused rings or ring systems;

[0189] Q² is an alkyl group, optionally substituted with one or morecycloalkyl or aryl groups, said Q² having from 1 to 30 carbons;

[0190] L′ is a monodentate or polydentate Lewis base, preferably L′ isreversibly coordinated to the metal complex such.that it may bedisplaced by an olefin monomer, more preferably L′ is a monodentateLewis base;

[0191] 1′ is a number greater than zero indicating the number of Lewisbase moieties, L′, and

[0192] Ar^(f) independently each occurrence is an anionic ligand group;preferably Ar^(f) is selected from the group consisting of halide, C₁₋₂₀halohydrocarbyl, and Q¹ ligand groups, more preferably Ar^(f) is afluorinated hydrocarbyl moiety of from 1 to 30 carbon atoms, mostpreferably Ar^(f) is a fluorinated aromatic hydrocarbyl moiety of from 6to 30 carbon atoms, and most highly preferably Ar^(f) is aperfluorinated aromatic hydrocarbyl moiety of from 6 to 30 carbon atoms.

[0193] Examples of the foregoing Group 13 metal salts are alumiciniumtris(fluoroaryl)borates or gallicinium tris(fluoroaryl)boratescorresponding to the formula: [M″Q¹ ₂L′_(1′)]⁺(Ar^(f) ₃BQ²)⁻, wherein M″is aluminum or gallium; Q¹ is C₁₋₂₀ hydrocarbyl, preferably C₁₋₈ alkyl;Ar^(f) is perfluoroaryl, preferably pentafluorophenyl; and Q² is C₁₋₈alkyl, preferably C₁₋₈ alkyl. More preferably, Q¹ and Q² are identicalC₁₋₈ alkyl groups, most preferably, methyl, ethyl or octyl.

[0194] The foregoing activating cocatalysts may also be used incombination. An especially preferred combination is a mixture of atri(hydrocarbyl)aluminum or tri(hydrocarbyl)borane compound having from1 to 4 carbons in each hydrocarbyl group or an ammonium borate with anoligomeric or polymeric alumoxane compound.

[0195] The molar ratio of catalyst/cocatalyst employed preferably rangesfrom 1:10,000 to 100:1, more preferably from 1:5000 to 10:1, mostpreferably from 1:1000 to 1:1. Alumoxane, when used by itself as anactivating cocatalyst, is employed in large quantity, generally at least100 times the quantity of metal complex on a molar basis.Tris(pentafluorophenyl)borane, where used as an activating cocatalyst isemployed in a molar ratio to the metal complex of form 0.5:1 to 10:1,more preferably from 1:1 to 6:1 most preferably from 1:1 to 5:1. Theremaining activating cocatalysts are generally employed in approximatelyequimolar quantity with the metal complex.

[0196] As an alternative method of activation, the metal complexes maybe exposed to electrochemical activation in the presence of a counterion. Such a technique is previously known in the art, and disclosed, forexample, in U.S. Pat. No. 5,372,682.

[0197] The catalysts, whether or not supported in any suitable manner,may be used to polymerize ethylenically unsaturated monomers having from2 to 100,000 carbon atoms either alone or in combination. Preferredaddition polymerizable monomers for use herein include olefins,diolefins and mixtures thereof. Preferred olefins are aliphatic oraromatic compounds containing vinylic unsaturation as well as cycliccompounds containing ethylenic unsaturation. Examples of the latterinclude cyclobutene, cyclopentene, norbornene, and norbornenederivatives that are substituted in the 5- and 6-positions with C₁₋₂₀hydrocarbyl groups. Preferred diolefins are C₄₋₄₀ diolefin compounds,including ethylidene norbornene; 1,4-hexadiene, and norbornadiene. Thecatalysts and processes herein are especially suited for use inpreparation of ethylene/1-butene, ethylene/1-hexene, ethylene/styrene,ethylene/propylene, ethylene/1-pentene, ethylene/4-methyl-1-pentene andethylene/1-octene copolymers as well as terpolymers of ethylene,propylene and a nonconjugated diene, such as, for example, EPDMterpolymers.

[0198] Most preferred monomers include the C₂₋₂₀ α-olefins, especiallyethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1decene, long chainmacromolecular α-olefins, and mixtures thereof. Other preferred monomersinclude styrene, C₁₋₄ alkyl substituted styrene, ethylidenenorbornene,1,4-hexadiene, 1,7-octadiene, vinylcyclohexane, 4-vinylcyclohexene,divinylbenzene, and mixtures thereof with ethylene. Long chainmacromolecular α-olefins are vinyl terminated polymeric remnants formedin situ during continuous solution polymerization reactions. Undersuitable processing conditions such long chain macromolecular units arereadily polymerized into the polymer product along with ethylene andother short chain olefin monomers to give small quantities of long chainbranching in the resulting polymer.

[0199] Preferred monomers include a combination of ethylene and one ormore comonomers selected from monovinyl aromatic monomers,4-vinylcyclohexene, vinylcyclohexane, norbornadiene,ethylidene-norbornene, C₃₋₁₀ aliphatic α-olefins (especially propylene,isobutylene, 1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene,and 1-octene), and C₄₋₄₀ dienes. Most preferred monomers are mixtures ofethylene and styrene; mixtures of ethylene, propylene and styrene;mixtures of ethylene, styrene and a nonconjugated diene, especiallyethylidenenorbornene or 1,4-hexadiene, and mixtures of ethylene,propylene and a nonconjugated diene, especially ethylidenenorbornene or1,4-hexadiene.

[0200] In general, the polymerization may be accomplished at conditionswell known in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions, that is, temperatures from 0-250° C.,preferably 30 to 200° C. and pressures from atmospheric to 10,000atmospheres. Suspension, solution, slurry, gas phase, solid state powderpolymerization or other process condition may be employed if desired. Asupport, especially silica, alumina, or a polymer (especiallypoly(tetrafluoroethylene) or a polyolefin) may be employed, anddesirably is employed when the catalysts are used in a gas phasepolymerization process. The support is preferably employed in an amountto provide a weight ratio of catalyst (based on metal):support from1:10⁶ to 1:10³, more preferably from 1:10⁶ to 1:10⁴.

[0201] In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10⁻¹²:1 to 10⁻¹:1,more preferably from 10⁻⁹:1 to 10⁻⁵:1.

[0202] Suitable solvents use for solution polymerization are liquidsthat are substantially inert under process conditions encountered intheir usage. Examples include straight and branched-chain hydrocarbonssuch as isobutane, butane, pentane, hexane, heptane, octane, andmixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; perfluorinated hydrocarbons such as perfluorinated C₄₋₁₀alkanes, and alkyl-substituted aromatic compounds such as benzene,toluene, xylene, and ethylbenzene. Suitable solvents also include liquidolefins which may act as monomers or comonomers.

[0203] The catalysts may be utilized in combination with at least oneadditional homogeneous or heterogeneous polymerization catalyst in thesame reactor or in separate reactors connected in series or in parallelto prepare polymer blends having desirable properties. An example ofsuch a process is disclosed in WO 94/00500.

[0204] The catalysts of the present invention are particularlyadvantageous for the production of ethylene homopolymers andethylene/α-olefin copolymers having high levels of long chain branching.The use of the catalysts of the present invention in continuouspolymerization processes, especially continuous, solution polymerizationprocesses, allows for elevated reactor temperatures which favor theformation of vinyl terminated polymer chains that may be incorporatedinto a growing polymer, thereby giving a long chain branch. The use ofthe present catalyst compositions advantageously allows for theeconomical production of ethylene/α-olefin copolymers havingprocessability similar to high pressure, free radical produced lowdensity polyethylene.

[0205] The present catalyst compositions may be advantageously employedto prepare olefin polymers having improved processing properties bypolymerizing ethylene alone or ethylene/α-olefin mixtures with lowlevels of a “H” branch inducing diene, such as norbornadiene,1,7-octadiene, or 1,9-decadiene. The unique combination of elevatedreactor temperatures, high molecular weight (or low melt indices) athigh reactor temperatures and high comonomer reactivity advantageouslyallows for the economical production of polymers having excellentphysical properties and processability. Preferably such polymerscomprise ethylene, a C₃₋₂₀ α-olefin and a “H”-branching comonomer.Preferably, such polymers are produced in a solution process, mostpreferably a continuous solution process.

[0206] The catalyst composition may be prepared as a homogeneouscatalyst by addition of the requisite components to a solvent or diluentin which polymerization will be conducted. The catalyst composition mayalso be prepared and employed as a heterogeneous catalyst by adsorbing,depositing or chemically attaching the requisite components on aninorganic or organic particulated solid. Examples of such solidsinclude, silica, silica gel, alumina, clays, expanded clays (aerogels),aluminosilicates, trialkylaluminum compounds, and organic or inorganicpolymeric materials, especially polyolefins. In a preferred embodiment,a heterogeneous catalyst is prepared by reacting an inorganic compound,preferably a tri(C₁₋₄ alkyl)aluminum compound, with an activatingcocatalyst, especially an ammonium salt of ahydroxyaryl(trispentafluorophenyl)borate, such as an ammonium salt of(4-hydroxy-3,5-ditertiarybutylphenyl)tris(pentafluorophenyl)borate or(4-hydroxyphenyl)-tris(pentafluoropheny This activating cocatalyst isdeposited onto the support by coprecipitating, imbibing, spraying, orsimilar technique, and thereafter removing any solvent or diluent. Themetal complex is added to the support, also by adsorbing, depositing orchemically attaching the same to the support, either subsequently,simultaneously or prior to addition of the activating cocatalyst.

[0207] When prepared in heterogeneous or supported form, the catalystcomposition is employed in a slurry or gas phase polymerization. As apractical limitation, slurry polymerization takes place in liquiddiluents in which the polymer product is substantially insoluble.Preferably, the diluent for slurry polymerization is one or morehydrocarbons with less than 5 carbon atoms. If desired, saturatedhydrocarbons such as ethane, propane or butane may be used in whole orpart as the diluent. Likewise, the α-olefin monomer or a mixture ofdifferent α-olefin monomers may be used in whole or part as the diluent.Most preferably, at least a major part of the diluent comprises theα-olefin monomer or monomers to be polymerized. A dispersant,particularly an elastomer, may be dissolved in the diluent utilizingtechniques known in the art, if desired.

[0208] At all times, the individual ingredients as well as the recoveredcatalyst components must be protected from oxygen and moisture.Therefore, the catalyst components and catalysts must be prepared andrecovered in an oxygen and moisture free atmosphere. Preferably,therefore, the reactions are performed in the presence of an dry, inertgas, such as, for example, nitrogen.

[0209] The polymerization may be carried out as a batchwise or acontinuous polymerization process. A continuous process is preferred, inwhich event catalyst, ethylene, comonomer, and optionally solvent, arecontinuously supplied to the reaction zone, and polymer productcontinuously removed therefrom.

[0210] Without limiting in any way the scope of the invention, one meansfor carrying out such a polymerization process is as follows: In astirred-tank reactor, the monomers to be polymerized are introducedcontinuously, together with solvent and an optional chain transferagent. The reactor contains a liquid phase composed substantially ofmonomers, together with any solvent or additional diluent and dissolvedpolymer. The reactor temperature and pressure may be controlled byadjusting the solvent/monomer ratio, the catalyst addition rate, as wellas by cooling or heating coils, jackets or any combination thereof. Thepolymerization rate is controlled by the rate of catalyst addition. Theethylene content of the polymer product is determined by the ratio ofethylene to comonomer in the reactor, which is controlled bymanipulating the respective feed rates of these components to thereactor. The polymer product molecular weight is controlled, optionally,by controlling other polymerization variables such as the temperature,monomer concentration, or by the previously mentioned chain transferagent, such as a stream of hydrogen introduced to the reactor, as iswell known in the art. The reactor effluent is contacted with a catalystkill agent such as water. The polymer solution is optionally heated, andthe polymer product is recovered by flashing off gaseous monomers aswell as residual solvent or diluent at reduced pressure, and, ifnecessary, conducting further devolatilization in equipment such as adevolatilizing extruder. In a continuous process the mean residence timeof the catalyst and polymer in the reactor generally is from 5 minutesto 8 hours, and preferably from 10 minutes to 6 hours.

[0211] Ethylene homopolymers and ethylene/α-olefin copolymers areparticularly suited for preparation according to the invention.Generally such polymers have densities from 0.85 to 0.96 g/ml. Typicallythe molar ratio of α-olefin comonomer to ethylene used in thepolymerization may be varied in order to adjust the density of theresulting polymer. When producing materials with a density range of from0.91 to 0.93 the comonomer to monomer ratio is less than 0.2, preferablyless than 0.05, even more preferably less than 0.02, and may even beless than 0.01. In the above polymerization process hydrogen has beenfound to effectively control the molecular weight of the resultingpolymer. Typically, the molar ratio of hydrogen to monomer is less than0.5, preferably less than 0.2, more preferably less than 0.05, even morepreferably less than 0.02 and may even be less than 0.01.

EXAMPLES

[0212] It is understood that the present invention is operable in theabsence of any component which has not been specifically disclosed. Thefollowing examples are provided in order to further illustrate theinvention and are not to be construed as limiting. Unless stated to thecontrary, all parts and percentages are expressed on a weight basis. Theterm “overnight”, if used, refers to a time of approximately 16-18hours, “room temperature”, if used, refers to a temperature of 20-25°C., and “mixed alkanes” refers to a mixture of hydrogenated propyleneoligomers, mostly C₆-C₁₂ isoalkanes, available commercially under thetrademark Isopar E™ from Exxon Chemicals Inc.

[0213] All solvents were purified using the technique disclosed byPangborn et al, Organometallics, 15, 1518-1520, (1996). ¹H and ¹³C NMRshifts were referenced to internal solvent resonances and are reportedrelative to TMS.

Example 1

[0214] (tetramethylcyclopentadienyl)dimethyl(t-butylamido)silanetitanium(II) bis(tri(methylsilyl))acetylene

[0215] 1.17 g (3.31 mmol)(tetramethylcyclopentadienyl)dimethyl(t-butylamido)titanium dichlorideand 1.70 g (10.0 mmol) bis(TMS)acetylene were dissolved in 50 mltoluene, followed by addition of 1.93 g (3.64 mmol) butylethylmagnesium.After 1 hour of refluxing the solution was filtered through a pad ofdiatomaceous earth and the solvent was removed under vacuum. Theresulting oil was redissolved in 10 ml hexane and filtered through a padof diatomaceous earth. The pad was washed with 10 ml hexane twice beforeall the solvent volume was reduced under vacuum and the solution placedin the freezer over night. The next morning the product was collected asa violet precipitate.

[0216]¹H NMR (C₆D₆): [ppm] δ=−0.03 (s, 18H, TMSC≡CTMS), 0.30 (s, 6H,Si(CH ₃)₂), 1.23, 2.65 (s, 12H, Cp(CH ₃)₄), 2.14 (s, 9H, t-Bu).

[0217]¹³C NMR (C₆D₆): [ppm] δ=1.28, 6.83, 13.07, 13.79, 38.08, 57.79,130.27, 133.64.

[0218] Polymerization General Conditions

[0219] Mixed alkanes and liquid olefins are purified by sparging withpurified nitrogen followed by passage through columns containing alumina(A-2, available from LaRoche Inc.) and Q5 reactant (available fromEnglehard Chemicals Inc.) at 50 psig using a purified nitrogen pad. Alltransfers of solvents and solutions described below are accomplishedusing a gaseous pad of dry, purified nitrogen or argon. Gaseous feeds tothe reactor are purified by passage through columns of A-204 alumina(available from LaRoche Inc.) and Q5 reactant. The aluminas arepreviously activated by treatment at 375° C. with nitrogen, and Q5reactant is activated by treatment at 200° C. with 5 percent hydrogen innitrogen.

[0220] Ethylene Polymerization

[0221] A stirred, two-liter Parr reactor was charged with approximately433 g of mixed hexanes. Hydrogen was added as a molecular weight controlagent by differential pressure expansion from a 75 mL addition tank at50 psig (345 kPa). The reactor was heated to 90° C. and saturated withethylene at 200 psig (1.4 MPa). The appropriate amount of catalyst andcocatalyst as 0.005M solutions in toluene were premixed in a gloveboxand transferred to a catalyst addition tank and injected into thereactor. After 10 minutes reaction with ethylene on demand the increasein reactor temperature was recorded and the reaction terminated.

[0222] The resulting solution was removed from the reactor into anitrogen purged collection vessel containing 100 ml of isopropyl alcoholand 20 ml of a 10 weight percent toluene solution of hindered phenolantioxidant (Irganox™ 1010 from Ciba Geigy Corporation) and phosphorusstabilizer (Irgafos™ 168 from Ciba Geigy Corporation). Polymers formedare dried in a programmed vacuum oven with a maximum temperature of 140°C. and a 20 hour heating period. The metal complex of the inventiondemonstrated from 10 to 50 percent improvement based on catalystefficiency over the comparative examples. The results are contained inTable 1. TABLE 1 Maximum Exoterm C₂H₄ flow Run Cat. (μmol) Cocatalyst(μmol) (° C.) (g/min) eff.¹ 1* TTTi² (2.5) FAB³ (7.5)/ 4.9 7.9 0.66 MAO⁴(25.0) 2  Ex. 1 (2.5) FAB³ (7.5)/ 5.6 38.5 0.74 MAO⁴ (25.0) 3* TTTi²(2.0) BAU⁵ (7.5)/ 8.3 26.3 0.66 MAO (20.0) 4  Ex. 1 (2.0) BAU⁵ (7.5)/28.9 59.5 1.00 MAO (20.0)

1. A metal complex corresponding to the formula: CpM(ZY)L (I), where Cpis a neutral or anionic ligand group containing at least on cyclic groupcontaining delocalized π-electrons, by means of which Cp is bonded to M;M is a metal selected from Groups 3-10 or the Lanthanide series of thePeriodic Table of the Elements; ZY is a linking group with Z bonded toCp and Y bonded to M, and wherein Z is SiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶ ₂, BR⁶, BR⁶L″, SnR⁶, or GeR⁶ ₂, and Y is —O—,—S—, —NR⁵—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂; R⁵, independently each occurrence,is hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl,said R⁵ having up to 20 atoms not counting hydrogen, and optionally twoR⁵ groups together with the remainder of Y form a ring system; R⁶,independently each occurrence, is hydrogen, or a member selected fromhydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl,—NR⁷ ₂, and combinations thereof, said R⁶ having up to 20 atoms notcounting hydrogen, and optionally, one or more R⁶ groups together withthe remainder of Z form a ring system; R⁷ independently each occurrenceis hydrocarbyl or two R⁷ groups together with N form a ring system, saidR⁷ having up to 10 atoms not counting hydrogen; L″ is a monodentate orpolydentate Lewis base optionally bonded to R⁶; and L is acetylene, or amono- or di-substituted derivative of acetylene.
 2. The metal complex ofclaim 1 wherein Cp is a cyclopentadienyl group or a hydrocarbylsubstituted derivative thereof.
 3. The metal complex of claim 1corresponding to the formula;

wherein M is a group 4 metal; Y is NR⁵, wherein R⁵ is C₁₋₁₀ alkyl orcycloalkyl; Z is dimethylsilane; J independently each occurrence ishydrogen, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl,halide, hydrocarbyloxy, trihydrocarbylsiloxy,bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino,hydrocarbyleneamino, hydrocarbylimino, di(hydrocarbyl)phosphino,hydrocarbylenephosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said J group having up to 40atoms not counting hydrogen atoms, and optionally two J groups togethermay form a divalent derivative thereby forming a saturated orunsaturated ring; and L is a disubstituted acetylene compound of theformula, J′C≡CJ′, wherein J′ is hydrocarbyl or tri(hydrocarbylsilyl) ofup to 10 atoms not counting hydrogen.
 4. The metal complex of claim 1selected from the group consisting of:(tetramethylcyclopentadienyl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,(tetramethylcyclopentadienyl)-N-(cyclohexyl)dimethylsilanamide titanium(II) 1,2-bis(trimethylsilyl)acetylene,(inden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (II)1,2-bis(trimethylsilyl)acetylene,(inden-1-yl)-N-(cyclohexyl)dimethylsilanamide titanium (II)1,2-bis(trimethylsilyl)acetylene,(2-methyl-4-phenylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,(2-methyl-4-phenylinden-1-yl)-N-(cyclohexyl)dimethylsilanamide titanium(II) 1,2-bis(trimethylsilyl)acetylene,(2-methyl4-naphthylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,(2-methyl4-naphthylinden-1-yl)-N-(cyclobexyl)dimethylsilanamide titanium(II) 1,2-bis(trimethylsilyl)acetylene,(3-(N,N-dimethylamino)inden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,(3-(N,N-dimethylamino)inden-1-yl)-N-(cyclohexyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,(3-(N,N-dimethylamino)inden-1-yl)-N-(1,1-dimethylethyl)dimeihylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,(3-(N-pyrrolidino)inden-1-yl)-N-(cyclohexyl)dimethylsilanamide titanium(II) 1,2-bis(trimethylsilyl)acetylene,(3-(N-pyrrolidino)inden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,(3-(N,N-dimethylamino)inden-1-yl)-N-(cyclohexyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,(s-indacen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (II)1,2-bis(trimethylsilyl)acetylene,(s-indacen-1-yl)-N-(cyclohexyl)dimethylsilanamide titanium (II)1,2-bis(trimethylsilyl)acetylene,(3,4-(cyclopenta(l)phenantrathen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,(3,4-(cyclopenta(l)phenantrathen-2-yl)-N-(cyclohexyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene,(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethylsilanamidetitanium (II) 1,2-bis(trimethylsilyl)acetylene, and mixtures thereof. 5.A catalyst for addition polymerizations comprising: A. i) a metalcomplex according to any one of claims 1-4, and ii) an activatingcocatalyst, the molar ratio of i) to ii) being from 1:10,000 to 100:1,or B. the reaction product formed by converting a metal complex of anyone of claims 1-4 to an active catalyst by use of the foregoingcombination or by use of an activating technique.
 6. The catalyst ofclaim 5 additionally comprising a support.
 7. A process for thepolymerization of addition polymerizable monomers comprising contactingthe monomer or mixture of monomers under polymerization conditions witha catalyst according to claim
 5. 8. A process for the polymerization ofaddition polymerizable monomers comprising contacting the monomer ormixture of monomers under polymerization conditions with a catalystaccording to claim
 6. 9. The process of claim 7 which is a solutionpolymerization process.
 10. The process of claim 8 which is a slurrypolymerization.
 11. The process of claim 8 which is a gas phasepolymerization.